WO1999052880A1 - Derives 5-iodo-4-phenethylaminopyrimidine, leurs intermediaires, procede de production associe, et pesticides agricoles et horticoles - Google Patents

Derives 5-iodo-4-phenethylaminopyrimidine, leurs intermediaires, procede de production associe, et pesticides agricoles et horticoles Download PDF

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Publication number
WO1999052880A1
WO1999052880A1 PCT/JP1999/001855 JP9901855W WO9952880A1 WO 1999052880 A1 WO1999052880 A1 WO 1999052880A1 JP 9901855 W JP9901855 W JP 9901855W WO 9952880 A1 WO9952880 A1 WO 9952880A1
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Prior art keywords
atom
group
compound
formula
pyrimidine
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PCT/JP1999/001855
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English (en)
Japanese (ja)
Inventor
Katsutoshi Fujii
Yoshinori Yamanaka
Kiyoshi Tsutsumiuchi
Youichi Yoshida
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Ube Industries, Ltd.
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Priority claimed from JP10241498A external-priority patent/JPH11292853A/ja
Priority claimed from JP10773198A external-priority patent/JP3903585B2/ja
Application filed by Ube Industries, Ltd. filed Critical Ube Industries, Ltd.
Priority to DE69933116T priority Critical patent/DE69933116T2/de
Priority to US09/673,494 priority patent/US6521627B1/en
Priority to EP99913576A priority patent/EP1074546B1/fr
Publication of WO1999052880A1 publication Critical patent/WO1999052880A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/30—Halogen atoms or nitro radicals

Definitions

  • the present invention relates to 5-phenodozole aminopyrimidine derivatives, intermediates thereof, their production methods and pesticides for agricultural and horticultural use.
  • the present invention relates to a novel 5-ododo 41-phenethylaminopyrimidine derivative which is useful as a pesticide for agricultural horticultural art, and a novel 4-chloro-5-ododo 6- ( ⁇ -substituted ethyl) which is an intermediate for producing the same.
  • the present invention relates to pyrimidine, a method for producing the same, and a pesticide for agricultural and horticultural use containing the derivative.
  • the 5-phospho-4-phenethylaminovirimidine derivative of the present invention is a novel compound and is not known to have pest control activity for agricultural pests.
  • An object of the present invention is to provide a novel 5-hydroxy-4-phenethylaminopyrimidine derivative, a method for producing the same, and a pesticide for agricultural and horticultural use containing the same as an active ingredient.
  • the inventors of the present invention have studied to solve the above-mentioned problems, and as a result, it has been found that a novel 5-ododo 41-phenethylaminobirimidine derivative is remarkable for insecticide, acaricide, nematicide and bactericidal activity for agriculture and horticulture. And completed the present invention.
  • the first invention has the following formula (1)
  • R 1 represents an octylogen atom, an alkoxy group having 2 to 4 carbon atoms or a hydroxyl group
  • R 2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon atom number. 1 to 4 haloalkyl groups, carbon atoms] to 4 alkoxy groups or 1 to 4 octaalkoxy groups
  • n is an integer of 1 to 3
  • * is asymmetric carbon Represents an atom
  • the present invention relates to a 5-phenyl-4-aminoethylaminopyrimidine derivative represented by the formula:
  • the second invention is a first invention.
  • R 2 and n are as defined above,
  • the third invention is
  • the fourth invention is a first invention.
  • R 3 represents a chlorine atom or a bromine atom
  • the fifth invention is a first invention.
  • R 4 represents an acyloxy group having 2 to 4 carbon atoms
  • the sixth invention is a first invention.
  • M represents alkali metal ⁇
  • the seventh invention is a first invention.
  • the eighth invention relates to a pesticidal agent for agricultural and solid agricultural arts, which comprises a 5-shodo-41-phenethylaminobilimidine derivative represented by the above formula (1) as an active ingredient.
  • R ′ is a halogen atom, an alkoxy group having 2 to 4 carbon atoms or a hydroxyl group,
  • octogen examples include chlorine, iodine, bromine, and fluorine, with chlorine and fluorine being preferred.
  • alkoxy group having 2 to 4 carbon atoms examples include those having a linear or branched alkyl group; an acetyloxy group is preferred.
  • R 2 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an octaalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carbon atom having 1 to 4 carbon atoms. There are four haloalkoxy groups.
  • halogen atom for R 2 examples include a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; a chlorine atom and a fluorine atom are preferred.
  • alkyl group having 1 to 4 carbon atoms examples include a linear or branched alkyl group, and a methyl group is preferable.
  • haloalkyl group having 1 to 4 carbon atoms examples include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2-fluoroethyl group, and the like; and more preferably, a trifluoromethyl group. is there.
  • alkoxy group having 1 to 4 carbon atoms examples include linear or branched ones; preferably, a methoxy group.
  • haloalkoxy group having 1 to 4 carbon atoms examples include difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, and 2-fluoroethoxy. But more preferably a trifluoromethoxy group or a 2,2,2-trifluoroethoxy group.
  • R 2 is preferably substituted at the m-position or the p-position.
  • n an integer of ⁇ to 3, with 1 or 2 being preferred.
  • Examples of the acid that forms an acid addition salt include, for example, inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, and phosphoric acid; formic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, sulfuric acid, aconit Carboxylic acids such as acids; methanesulfonic acid, benzenesulfonic acid, sulfonic acids such as p-toluenesulfonic acid; saccharin and the like.
  • the compound (1) or (2) of the present invention contains an asymmetric carbon atom indicated by *, any of the individual optical isomers, racemates, and mixtures thereof derived from these are also included in the present invention. It is.
  • Examples of the compound (1) include compounds obtained by combining the above-mentioned various fi-substituents.
  • Preferred compounds from the viewpoint of medicinal properties are as follows.
  • R 1 is an acyl group having 2 to 4 carbon atoms
  • R 2 is a hydrogen atom (1).
  • Examples of the compound (2) which is a synthetic intermediate of the compound (1) include those having a preferable substituent of R 1 described above.
  • R 2 , ⁇ and * are as defined above;
  • R 3 represents a chlorine atom or a bromine atom;
  • a 4-phenethylaminovirimidine derivative (referred to as compound (111)) represented by
  • R 4 represents a lower acyloxy group
  • R 2 , R 4 , n and * are as defined above,
  • a 4-phenethylaminopyrimidine derivative represented by the above formula (112) (referred to as compound (112));
  • M represents an alkali metal
  • R 2 , n and * are as defined above,
  • R 2 , R 3 , ⁇ , and * are as defined above,
  • a 4-phenethylaminovirimidine derivative (referred to as compound (111)) represented by the following formula (9):
  • a method for producing a 5-odo-4 phenethylaminovirimidine derivative (referred to as compound (114)) represented by the above formula (114), characterized by reacting
  • the synthesis methods 1 to 5 of the compound (1) of the present invention will be described in more detail.
  • Synthesis method 1 is a method of reacting compound (2) with compound (3) in a solvent in the presence of a base to obtain compound (1).
  • the type of the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • the solvent include benzene, toluene, xylene, methylnaphthalene, petroleum ether, rig mouth, hexane, chlorobenzene, dichlorobenzene, and the like.
  • Chlorinated or unchlorinated aromatic, aliphatic and cycloaliphatic hydrocarbons such as formaldehyde, dichloroethane, and trichloroethylene
  • ethers such as tetrahydrofuran, siloxane, and dimethyl ether
  • Nitrils such as ril and propionitol, ketones such as acetone and methylethylketone, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, N, N-dimethylimidazo
  • Non-protonic solvents such as lysinone, N-methylpyrrolidone; And the like mixed compounds of the solvent.
  • the solvent can be used in such an amount that the compound (2) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.
  • the type of base is not particularly limited, and organic and inorganic bases, for example, tertiary amines such as triethylamine, organic bases such as DBU, alkali metal and alkaline earth metal hydrides, hydroxides, and carbonates Inorganic bases such as salts and bicarbonates can be mentioned; organic bases such as triethylamine are preferred.
  • organic and inorganic bases for example, tertiary amines such as triethylamine, organic bases such as DBU, alkali metal and alkaline earth metal hydrides, hydroxides, and carbonates
  • organic bases such as triethylamine are preferred.
  • the amount of the base to be used is 1 to 5 moles relative to compound (2); preferably, it is 1.2 to 2.0 moles.
  • the reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent to be used or lower; preferably 60 to 110.
  • the reaction time varies depending on the temperature and temperature described above; it is usually 0.5 to 5 hours.
  • the amount of the starting compound used is 1.0 to 5 times mol of compound (3) with respect to compound (2); preferably 1 to 1.1 times mol.
  • the compound (2) used in the present invention can be produced by the method shown in the following formula.
  • R 3 , R 4 , M and * have the same meanings as described above;
  • DAST represents getylaminosulfate trifluorofluoride.
  • Compound (4) can be produced, for example, by the method shown in the following formula, according to the method described in Journal Journal of Chemical Society (JCS) 3478-3481 (1955).
  • Compound (3) can be a commercially available product or can be produced by the method shown in the following formula.
  • the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, shrinkage, and mouth extraction, and if necessary, recrystallization, various chromatography, etc. It can be appropriately purified by means.
  • Examples of the type of the solvent include ethers, ketones, and amides such as N, N-dimethylacetoamide described in Synthetic Method 1; 1,3-dimethyl-2-imidazolidone, sulfolane, dimethyl sulfoxide; Mixtures of the above solvents may be mentioned; N, N-dimethylformamide of the amides is preferred.
  • the solvent can be used in such an amount that the compound (111) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.
  • Examples of the type of base include the inorganic bases described in Synthesis Method 1; potassium carbonate is preferred.
  • the amount of the base to be used is 1 to 5 moles per 1 mole of the compound (111); preferably 2 to 5 moles.
  • the reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower; preferably 60 to 100.
  • the reaction time varies depending on the temperature and temperature described above, but is 0.5 to 8 hours.
  • a commercially available product can be used as the daggered product (4).
  • the target compound (1-2) produced as described above is subjected to ordinary post-treatments such as extraction, reduction, filtration, etc., and, if necessary, recrystallization and various chromatographic methods. It can be appropriately purified by known means such as.
  • Synthetic method 3 is a method of reacting compound (112) with compound (5) in a solvent to obtain compound (113).
  • Examples of the type of the solvent include ethers, ketones, amides, alcohols (methanol, ethanol, propanol, butanol, etc.), water, and a mixture of the above solvents, as described in Synthesis Method 1.
  • a mixture of alcohols (methanol, ethanol) and water is preferred.
  • the solvent can be used in such an amount that the compound (1-2) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.
  • Examples of the compound (5) include commercially available inorganic bases described in Synthetic Method 1; preferably, sodium hydroxide and hydroxylamylium are used.
  • the amount of the base to be used is 1 to 2 moles per 1 mole of the compound (1-2); preferably ⁇ 1.5 times the moles.
  • the reaction temperature is in the temperature range from 0 to room temperature; room temperature is preferred.
  • the reaction time varies depending on the concentration and temperature of the previous IE; 0.5 to 3 hours.
  • the target compound (1-3) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, filtration, etc., and if necessary, recrystallization, various types of chromatography, etc. Can be appropriately purified by the means described above.
  • Synthesis method 4 is a method of reacting compound (1-3) with compound (6) in a solvent or without solvent to obtain compound (114).
  • Solvent types include chlorinated or unchlorinated aromatic, aliphatic, alicyclic hydrocarbons, ethers, etc. as described in Synthesis Method 1; chlorine, such as dichloromethane. Aliphatic hydrocarbons are preferred.
  • the amount of the solvent to be used may be such that the compound (1-2) is 5 to 80% by weight; it is preferably 10 to 70% by weight.
  • the reaction temperature is not particularly limited, but is in the temperature range from room temperature to the boiling point of the solvent used or less; 0 to room temperature is preferred.
  • the reaction time varies depending on the concentration and the temperature, but is 0.5 to 1 hour.
  • the compound (6) is not particularly limited, but is preferably a commercially available product such as the above-mentioned getylaminosulfur trifluoride (DAST).
  • the amount of compound (6) to be used is 1 to 2 moles relative to compound (1 to 2); preferably 1 to 1.5 moles.
  • the target compound (1-3) produced as described above is subjected to ordinary post-treatments such as extraction, lysis, filtration, etc., and if necessary, recrystallization, various chromatographies, etc. Can be appropriately purified by known means.
  • Examples of the type of the solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide; 1,3-dimethyl-2-imidazolidone, sulfolane, dimethyl sulfoxide; and mixtures of the above solvents. be able to.
  • the amount of the solvent to be used may be such that the compound (14) is 5 to 80% by weight; it is preferably 10 to 70% by weight.
  • the reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent to be used or lower; preferably from 100 to 12 O ⁇ C.
  • the reaction time varies depending on the concentration and temperature as described above; it is 1 to 15 hours.
  • potassium fluoride sodium fluoride and cesium fluoride
  • potassium fluoride and cesium fluoride are preferable.
  • the amount of the compound (7) to be used is 1 to 5 moles, preferably 1 to 3 moles, per 1 mole of the aldehyde compound (111).
  • the target compound (14) produced as described above is subjected to ordinary post-treatments such as extraction, contraction, and filtration, and if necessary, recrystallization, various chromatographies, etc. Can be appropriately purified by known means of
  • Synthesis method 6 is a method of reacting compound (4) with compound (5) in a solvent to obtain compound (2-11).
  • the type of the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • the solvent include benzene, toluene, xylene, methylnaphthalene, petroleum ether, rig mouth, hexane, chlorobenzene, dichlorobenzene, and the like.
  • Chlorinated or unchlorinated aromatic, aliphatic, and alicyclic hydrocarbons such as formaldehyde, dichloromethane, dichloroethane, and trichloroethylene; tetrahydrofuran, cyanoxane, and dimethyl ether
  • chlorinated aliphatic hydrocarbons such as chloroform, dichloromethane and dichloroethane.
  • the amount of the solvent used may be such that the amount of the arsenic compound (4) is 5 to 80% by weight; it is preferably 10 to 70% by weight.
  • the reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower; preferably from 10 to 30.
  • the reaction time varies depending on the temperature and temperature as described above; it is usually 0.5 to 5 hours.
  • the compound (5) is used in a molar amount of 1,0 to 5 times, and preferably in a molar amount of 1 to 1.3 times, relative to the compound (4).
  • the compound (4) used in the present invention can be produced, for example, according to the method described in Journal Saibu, Chemical Society (JCS) 3478-3481 (1955).
  • the target compound (2-1) produced as described above is subjected to ordinary post-treatments such as extraction, shrinkage, and mouth-flow, and if necessary, distillation, recrystallization, and various chromatographies. It can be appropriately purified by a known means such as graphy. (Synthesis method 7)
  • the solvent examples include ethers, ketones, amides such as N, N-dimethylacetamide; 1,3-dimethyl-2-imidazolidone, sulfolane, dimethyl sulfoxide; and mixtures of the above solvents.
  • amides N, N-dimethylformamide are preferred.
  • the solvent can be used in such an amount that the compound (2-1) is 5 to 80% by weight; however, it is preferably 10 to 70% by weight.
  • the type of base is not particularly limited, and organic and inorganic bases, for example, tertiary amines such as triethylamine, organic bases such as DBU, alkali metal and alkaline earth metal hydrides, hydroxides, and carbonates Inorganic bases such as salts and bicarbonates can be mentioned; preferably, the carbonate base of the inorganic base is used.
  • organic and inorganic bases for example, tertiary amines such as triethylamine, organic bases such as DBU, alkali metal and alkaline earth metal hydrides, hydroxides, and carbonates
  • Inorganic bases such as salts and bicarbonates can be mentioned; preferably, the carbonate base of the inorganic base is used.
  • the amount of the base to be used is 1 to 5 moles relative to compound (2-1); preferably 2 to 5 moles.
  • the reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent used or lower; preferably 50 to 100.
  • reaction time varies depending on the temperature and temperature as described above;
  • the compound (6) a commercially available product can be used.
  • the target compound (2-2) produced as described above is subjected to ordinary post-treatments such as extraction, lysis, filtration, etc., and if necessary, recrystallization, various chromatographies, etc. Can be appropriately purified by known means.
  • Synthetic method 8 is a method of reacting compound (2-2) with compound (7) in a solvent to obtain compound (213).
  • Examples of the type of the solvent include alcohols such as methanol, ethanol, propanol, and butanol; ditriles such as acetate and propionitol; ketones such as acetone and methylethyl ketone. , Aprotic polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, sulfolane, N, N-dimethylimidazolidinone, N-methylpyrrolidone, water; and mixtures of the above solvents. But a mixture of alcohols (methanol, ethanol) and water is preferred.
  • the amount of the solvent used may be such that the compound (2-2) is 5 to 80% by weight; it is preferably 10 to 70% by weight.
  • Examples of the compound (7) include inorganic bases such as sodium hydroxide and potassium hydroxide; and hydroxyl: sodium.
  • the amount of the compound (7) to be used is 1 to 2 moles compared to the compound (2-2); preferably 1 to 1.5 moles.
  • the reaction temperature is within a temperature range of from 0 to the boiling point of the solvent used or less; room temperature to 50 is preferred.
  • the reaction time varies depending on the temperature and temperature as described above, but is 0.5 to 3 hours.
  • the target compound (2-3) produced as described above is subjected to ordinary post-treatments such as extraction, port reduction, and filtration, and if necessary, recrystallization, various types of chromatography, etc. Can be appropriately purified by the means described above.
  • Synthesis method 9 is a method of reacting compound (2-3) with compound (8) in a solvent or without solvent to obtain compound (2-4).
  • Solvent types include chlorinated or unchlorinated aromatic, aliphatic, alicyclic hydrocarbons, ethers, etc .; chlorinated aliphatic hydrocarbons Dichloromethane is preferred.
  • the amount of the solvent to be used may be such that the compound (2-3) is 5 to 80% by weight; it is preferably 10 to 70% by weight.
  • the reaction temperature is not particularly limited, but is in the range of room temperature to the boiling point of the solvent to be used or lower;
  • the reaction time varies depending on the degree of port and temperature as described above;
  • the compound (8) is not particularly limited; however, the aforementioned commercially available getylaminosulfur trifluoride (DAST) is preferred.
  • the amount of the compound (8) to be used is 1 to 2 moles compared to the compound (2-3); preferably 1 to 1.5 moles.
  • the target compound (2-4) produced as described above is subjected to ordinary post-treatments such as extraction, port reduction, and filtration, and if necessary, recrystallization, various chromatographies, etc. Can be appropriately purified by known means.
  • the pests for agricultural and solid cultivation which are controlled by the compound (1) of the present invention include agricultural painting pests (for example, Hemiptera (Pteropoda, leafhoppers, aphids, whiteflies, etc.), Lepidoptera (Coleoptera, Scarabaeidae, Coleoptera, Pests, Scarabaeidae, Calyptera, etc.), Coleoptera (Coleoptera, Tenebrionidae, Rotifers, Scarabaeidae, etc.) Two families of red mites, Namihadani, etc., and two families of the family Acarinae, etc.)), nematodes (Nematoda, Cystina, Negusa) Mosquitoes, singaresenthus, pine wood moss, etc., spider mites, hygiene pests (eg, flies, power, cockroaches, etc.), storage pests (eg, coccinaceae, mamezodushi
  • the pesticidal agent for agricultural and horticultural use according to the present invention has remarkable insecticidal / miticidal and nematicidal effects, and contains at least one compound (1) as an active ingredient.
  • the compound (1) can be used alone, but it is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent, and the like (for example, powder, emulsion, fine granule, granule, water Prepared as a composition such as a wetting agent, an oily suspension, or an aerosol).
  • a carrier for example, a surfactant, a dispersant, an auxiliary agent, and the like (for example, powder, emulsion, fine granule, granule, water Prepared as a composition such as a wetting agent, an oily suspension, or an aerosol).
  • the carrier examples include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, cas sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexane, etc.) Hexanone, isophorone, etc., esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.) ),
  • surfactants and dispersants that can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement in absorption, dispersion of drugs, emulsification, and spreading, include alcohol esters, alkyl sulfonic acids, and the like. Salts, lignin sulfonates, polyoxyethylene glycol ethers and the like can be mentioned.
  • carboxymethylcellulose, polyethylene glycol, arabia gum and the like can be used as adjuvants.
  • the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in appropriate combination, respectively, according to the respective purposes.
  • the concentration of the active ingredient is usually about 50% by weight for emulsions, usually 0.3 to 25% by weight for powders, and usually 1 to 90% by weight for wettable powders. Usually, 0.5-5% by weight for granules, 0.5-5% by weight for oils, and 0.5-5% by weight for aerosols. Always 0.1 to 5% by weight.
  • preparations can be diluted to an appropriate degree and applied to various uses by spraying them on the water surface of plants, leaves, soil and paddy fields, or directly applying them, depending on the purpose.
  • Table 1 shows the compounds (2) synthesized as described above and their physical properties.
  • Table 2 shows the compounds (1) synthesized as described above and their physical properties.
  • Toxanone (trade name, manufactured by Sanyo Chemical Industries) was added to 20 parts by weight of compound (1) and 70 parts by weight of xylene, and the mixture was uniformly mixed and dissolved to obtain an emulsion.
  • Compound (1) was uniformly mixed with 5 parts by weight of powder, 50 parts by weight of talc, and 45 parts by weight of kaolin to obtain a powder.
  • Example 4 (Efficacy test)
  • Each wettable powder of the compound (1) shown in Tables 2 and 3 prepared according to Example 2 was diluted with water to 30 Opm, 0.1 ml of which was placed in a test tube, and then added to a test tube. 0.9 ml of liquid containing 500 heads was added.
  • test tubes were released into a low-temperature room at 25 ° C, and observed 2 days later under a microscope to determine the nematicidal rate.
  • Each of the wettable powders prepared in accordance with Example 2 was diluted with water containing (0.01%) a surfactant to 300 ppm, and added to each of these solutions. After fifteen female female adults were produced for 24 hours, they were immersed for 10 seconds in each of the leaves of the wings (diameter 2 Omm) from which the adults were removed.
  • each leaf piece was left in a constant temperature room at 25, and three days later, the number of live and dead insects on each leaf piece was counted to determine the acaricidal rate.
  • Each wettable powder of the compound (1) shown in Tables 2 and 3 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%), and the cabbage was added to each of these chemical solutions.
  • Leaf pieces (5 cm ⁇ 5 cm) were immersed for 30 seconds, placed in each plastic cup, and air-dried.
  • Each wettable powder of compound (1) shown in Tables 2 and 3 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%), and the rice solution was added to each of these chemical solutions.
  • the seedlings were soaked for 30 seconds, air-dried, and inserted into each glass cylinder.
  • Each wettable powder of the compound (1) shown in Tables 2 and 3 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%). Rice seedlings were immersed for 30 seconds, air-dried, and inserted into respective glass cylinders.
  • Each wettable powder of the compound (1) shown in Tables 2 and 3 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%).
  • the soybean leaves were crushed by S for 30 seconds, air-dried, placed in plastic cups, and 10 each of the lotus spruce (second instar larvae) were released, covered, and left in a constant temperature room at 25 ° C. Two days later, the number of live and dead insects was counted to determine the mortality.
  • a wheat plant (cultivar: Kobushi barley) was grown 10 per plant in a 6 cm-diameter plastic flowerpot and prepared according to Example 2 to a 1.5-leaf seedling.
  • the wettable powder of the product (1) shown in Tables 2 and 3 was diluted to 500 ppm with water containing a surfactant (0.01%) and sprayed at 20 ml per pot. .
  • the plants were cultivated in a glass greenhouse for 2 days, and then a spore suspension (7 ⁇ 10 4 spores Zm I) of the Fusarium head blight fungus was uniformly sprayed on the plant body for 3 minutes.
  • the plants were grown for one week in a glass greenhouse, and the extent of the leaf spot on the first leaf of the wheat was examined.
  • novel 5-hydroxy-4-phenethylaminopyrimidine derivative of the present invention is useful as a pesticide for agricultural and horticultural use.
  • novel 4-chloro-5-odo-6- ( ⁇ -substituted ethyl) pyrimidine of the present invention is useful as an intermediate for pharmaceuticals, agricultural chemicals and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des nouveaux dérivés 5-iodo-4-phénéthylaminopyrimidine, représentés par la formule générale suivante (1), ainsi que des pesticides contenant ces dérivés. Dans cette formule, R1 représente halogéno, acyloxy C¿2-4? ou hydroxy, R?2¿ représente hydrogène, halogéno, alkyle C¿1-4?, haloalkyle C1-4, ou alcoxy C1-4 ou haloalcoxy C1-4, n représente un nombre entier compris entre 1 et 3 et * représente un atome de carbone asymétrique.
PCT/JP1999/001855 1998-04-14 1999-04-08 Derives 5-iodo-4-phenethylaminopyrimidine, leurs intermediaires, procede de production associe, et pesticides agricoles et horticoles WO1999052880A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69933116T DE69933116T2 (de) 1998-04-14 1999-04-08 5-iod-4-phenylethylaminopyrimidin-derivate, zwischenverbindungen davon, verfahren zu ihrer herstellung und pestizide für landwirtschaft und gartenbau
US09/673,494 US6521627B1 (en) 1998-04-14 1999-04-08 5-Iodo-4-phenethylaminopyrimidine derivative, intermediate thereof, processes for producing the same and agricultural and horticultural pesticides
EP99913576A EP1074546B1 (fr) 1998-04-14 1999-04-08 Derives 5-iodo-4-phenethylaminopyrimidine, leurs intermediaires, procede de production associe, et pesticides agricoles et horticoles

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP10/102414 1998-04-14
JP10241498A JPH11292853A (ja) 1998-04-14 1998-04-14 ４−クロロ−５−ヨード−６−（α−置換エチル）ピリミジン及びその製法
JP10773198A JP3903585B2 (ja) 1998-04-17 1998-04-17 ５−ヨード−４−フェネチルアミノピリミジン誘導体、その製法及び農園芸用の有害生物防除剤
JP10/107731 1998-04-17

Publications (1)

Publication Number Publication Date
WO1999052880A1 true WO1999052880A1 (fr) 1999-10-21

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PCT/JP1999/001855 WO1999052880A1 (fr) 1998-04-14 1999-04-08 Derives 5-iodo-4-phenethylaminopyrimidine, leurs intermediaires, procede de production associe, et pesticides agricoles et horticoles

Country Status (4)

Country Link
US (1) US6521627B1 (fr)
EP (1) EP1074546B1 (fr)
DE (1) DE69933116T2 (fr)
WO (1) WO1999052880A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE414694T1 (de) * 2005-05-03 2008-12-15 Bayer Cropscience Sa Neue heterocyclylethylbenzamid-derivate
ES2443154T3 (es) 2009-07-16 2014-02-18 Sds Biotech K. K. Derivados de 4-(3-butinil) aminopirimidina como agentes pesticidas para uso agrícola y hortícola

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0370391A2 (fr) * 1988-11-21 1990-05-30 Lonza Ag Procédé de préparation de 4,5-dichloro-6-éthylpyrimidine
JPH07118242A (ja) * 1993-10-26 1995-05-09 Ube Ind Ltd フェノキシアルキルアミン誘導体、その製法及び農園芸用の有害生物防除剤
JPH07258223A (ja) * 1994-02-01 1995-10-09 Ube Ind Ltd ４−フェネチルアミノピリミジン誘導体、その製法及び農園芸用の有害生物防除剤
JPH08291149A (ja) * 1995-04-21 1996-11-05 Ube Ind Ltd ４−〔２−（トリフルオロアルコキシ置換フェニル）エチルアミノ〕ピリミジン誘導体、その製法及び農園芸用の有害生物防除剤

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BG94957A (bg) 1990-08-10 1993-12-24 Ciba - Geigy Ag Пиримидинови производни и средство за борба срещу вредители по растенията
EP0665225B1 (fr) 1994-02-01 1996-11-27 Ube Industries, Ltd. 4-Phénylaminopyrimidines, procédé pour leur préparation et pesticides pour l'agriculture et l'horticulture les contenant
JPH1036355A (ja) * 1996-07-19 1998-02-10 Ube Ind Ltd ４−アミノ−５−クロロ−６−（１−フルオロエチル）ピリミジン誘導体の製法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0370391A2 (fr) * 1988-11-21 1990-05-30 Lonza Ag Procédé de préparation de 4,5-dichloro-6-éthylpyrimidine
JPH07118242A (ja) * 1993-10-26 1995-05-09 Ube Ind Ltd フェノキシアルキルアミン誘導体、その製法及び農園芸用の有害生物防除剤
JPH07258223A (ja) * 1994-02-01 1995-10-09 Ube Ind Ltd ４−フェネチルアミノピリミジン誘導体、その製法及び農園芸用の有害生物防除剤
JPH08291149A (ja) * 1995-04-21 1996-11-05 Ube Ind Ltd ４−〔２−（トリフルオロアルコキシ置換フェニル）エチルアミノ〕ピリミジン誘導体、その製法及び農園芸用の有害生物防除剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1074546A4 *

Also Published As

Publication number Publication date
DE69933116D1 (de) 2006-10-19
US6521627B1 (en) 2003-02-18
EP1074546A4 (fr) 2001-07-18
EP1074546B1 (fr) 2006-09-06
DE69933116T2 (de) 2007-04-12
EP1074546A1 (fr) 2001-02-07

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